Copper foil for producing graphene and method of producing graphene using the same

ABSTRACT

A copper foil for producing graphene, having 60 degree gloss of 500% or more in a rolling direction and a direction transverse to the rolling direction, and an average crystal grain size of 200 μm or more after heating at 1000° C. for 1 hour in an atmosphere containing 20% by volume or more of hydrogen and balance argon.

FIELD OF THE INVENTION

The present invention relates to a copper foil base for producinggraphene, and a method of producing graphene using the same.

DESCRIPTION OF THE RELATED ART

Graphite has a layered structure where a plurality of layers of carbonsix-membered rings planarly arranged is laminated. The graphite having amono atomic layer or around several atomic layers is called as grapheneor a graphene sheet. The graphene sheet has own electrical, optical andmechanical properties, and in particularly has a high carrier mobilityspeed. Therefore, the graphene sheet has expected to be applied invarious industries as a fuel cell separator, a transparent electrode, aconductive thin film for a display device, a “mercury-free” fluorescentlamp, a composite material, a carrier for Drug Delivery System (DDS)etc.

As a method of producing the graphene sheet, it is known that graphiteis peeled with an adhesion tape. However, there are problems in that thenumber of the layer(s) of the graphene sheet obtained is not uniform, awide area graphene sheet is difficult to be provided, and it is notsuitable for mass production.

A technology has been developed that a sheet-like monocrystalgraphitized metal catalyst is contacted with a carboneous substance andthen is heat treated to grow the graphene sheet (Chemical VaporDeposition (CVD) method) (Patent Literature 1). As the monocrystalgraphitized metal catalyst, there is described a metal substrate made ofNi, Cu or W, for example.

Similarly, a technology has been reported that a graphene film is formedby the chemical vapor deposition method on a copper layer formed on anNi or Cu metal foil or an Si substrate. The graphene film is formed atabout 1000° C. (Non-Patent Literature 1).

PATENT LITERATURE

[Patent Literature 1] Japanese Unexamined Patent Publication (Kokai)2009-143799

PATENT LITERATURE

[Non-Patent Literature 1] SCIENCE Vol. 324 (2009) P1312-1314

Problems to be Solved by the Invention

However, it is not easy and spends high costs to produce the monocrystalmetal substrate, a wide area substrate is difficult to be provided, anda wide area graphene sheet is thus difficult to be provided, asdescribed in Patent Document 1. On the other hand, Non-Patent Document 1describes that Cu is used as the substrate. Graphene is not grown on acopper foil in a plane direction within a short time. A Cu layer formedon an Si substrate is annealed to provide coarse grains, therebyproviding a substrate. In this case, a size of graphene is limited tothe size of the Si substrate, and its production costs are high, too.

Specifically, an object of the present invention is to provide a copperfoil for producing graphene being capable of producing graphene having alarge area with low costs, and a method of producing graphene using thesame.

Means for Solving the Problems

A first aspect of the present invention provides a copper foil forproducing graphene, having 60 degree gloss of 500% or more in a rollingdirection and a direction transverse to the rolling direction, and anaverage crystal grain size of 200 μm or more after heating at 1000° C.for 1 hour in an atmosphere containing 20% by volume or more of hydrogenand balance argon.

Preferably, the average crystal grain size is 400 μm or more. Morepreferably, the average crystal grain size is 900 μm or more.Preferably, a superficial arithmetic mean roughness Ra is 0.05 μm orless.

A second aspect of the present invention provides a copper foil forproducing graphene, having a superficial arithmetic mean roughness Ra is0.05 μm or less. Preferably, the arithmetic mean roughness Ra is 0.03 μmor less.

Preferably, the copper foil for producing graphene of the presentinvention consists of tough pitch copper in accordance withJIS-H3100-2000 or JIS-H3250-2000; or consists of oxygen free copper inaccordance with JIS-H3100-2000 or JIS-H3510-1992, or contains 0.050% bymass or less of one or more of elements selected from the groupconsisting of Sn and Ag to the tough pitch copper or the oxygen freecopper.

Further, the present invention provides a method of producing graphemegraphene using the copper foil for producing graphene according to anyone of Claims 1 to 7 the present invention, comprising the steps of:providing a carbon-containing gas while placing the heated copper foilto form graphene on a surface of the copper foil for producing graphene;laminating a transfer sheet on the surface of the graphene, and etchingand removing the copper foil for producing graphene while transferringthe graphene to the transfer sheet.

Effect of the Invention

According to the present invention, there can be provided a copper foilbeing capable of producing graphene having a large area with low costs.

BRIEF DESCRIPTION OF DRAWING

FIG. 1 A process chart showing a method of producing graphene accordingto an embodiment of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hereinafter, a copper foil for producing graphene according to anembodiment of the present invention will be described. The symbol “%”herein refers to % by mass, unless otherwise specified.

Composition

As the copper foil for producing graphene, tough pitch copper (TPC) inaccordance with JIS-H3250-2000 or JIS-H3100-2000 or oxygen free copper(OFC) in accordance with JIS-H3510-1992 or JIS-H3100-2000 can be used.

In addition, to the tough pitch copper or the oxygen free copper, acomposition containing 0.050% by mass or less of one or more of elementsselected from the group consisting of Sn and Ag can be used. When theabove-described elements are contained, the copper foil can haveimproved strength and adequate elongation, and the grain size can beincreased. If a content percentage of the above-described elementsexceeds 0.050% by mass, the strength may be further increased, but theelongation may be decreased to degrade workability and suppress thegrowth of the grain size. More preferably, the content percentage of theabove-described elements is 0.040% by mass or less.

Although a lower limit of the content percentage of the above-describedelements is not especially limited, the lower limit may be 0.005% bymass, for example. If the content percentage of the above-describedelements is less than 0.005% by mass, the content percentage may bedifficult to be controlled.

Thickness

The thickness of the copper foil for producing graphene is notespecially limited, but is generally 5 to 150 μm. Preferably, thethickness of the copper foil is 12 to 50 μm for ease of etching andremoval as described later while assuring handleability. If thethickness of the copper foil for producing graphene is less than 12 μm,it may be easily broken and have less handleability. If the thicknessexceeds 50 μm, etching and removal may be difficult.

60 Degree Gloss

60 degree gloss (JIS Z8741-1997) of the copper foil for producinggraphene is 500% or more both in a rolling direction and a directiontransverse to rolling direction.

As described later, after graphene is produced using the copper foil forproducing graphene according to the present invention, the graphene isneeded to be transferred from the copper foil to a transfer sheet. It isfound that when a surface of the copper foil is rough, it is difficultto transfer the graphene, and the graphene is broken. As an indicatorfor representing a surface irregularity of the copper foil, 60 degreegloss is specified.

When the 60 degree gloss in a rolling direction or a directiontransverse to rolling direction is less than 500%, the graphene isbroken upon the transfer. An upper limit of the 60 degree gloss in arolling direction or a direction transverse to rolling direction is notespecially limited, but about 800% is practically the upper limit.

In addition, in order to ease the transfer of the graphene to thetransfer sheet, the surface of the copper foil for producing graphenehas an arithmetic mean roughness Ra in accordance with JIS B0601-1994 ofpreferably 0.05 μm or less, and more preferably 0.03 μm or less.Although a lower limit of the Ra is not needed to be especially limited,it is considered that the lower limit value of the Ra on the surface ofthe copper foil that can be produced is about 0.01 μm.

Average Crystal Grain Size

After the cooper foil for producing graphene is heated at 1000° C. for 1hour in an atmosphere containing 20% by volume or more of hydrogen andbalance argon, an average crystal grain size thereof is 200 μm or more.

If the average crystal grain size of the cooper foil for producinggraphene is less than 200 μm, it makes an obstacle for growth of thegraphene on the surface of the copper foil for producing graphene, andthe graphene is difficult to be grown in a planar direction. It maybecause a crystal grain boundary makes the obstacle for the growth ofthe graphene. In particular, the average crystal grain size of thecopper foil for producing graphene is preferably 900 μm or more.

The heating at 1000° C. for 1 hour in an atmosphere containing 20% byvolume or more of hydrogen and balance argon is simulated for acondition of heating the copper foil for producing graphene at adecomposition temperature of the carbon-containing gas or more, whengraphene is produced.

Further, the average crystal grain size is determined by measuring thecopper foil for producing graphene with a cutting method by JISH0501-1986.

Using the copper foil for producing graphene as specified above, thelarge-area graphene can be produced at low costs and a high yield.

Production of Copper Foil for Producing Graphene

The copper foil for producing graphene according to the embodiment ofthe present invention can be produced as follows, for example: Firstly,a copper ingot having a predetermined composition is produced, is hotrolled, and is annealed and cold rolled repeatedly to provide a rolledsheet. The rolled sheet is annealed to be re-crystallized, and finallycold rolled to the predetermined thickness of a rolling reduction of 80to 99.9% (preferably 85 to 99.9%, more preferably 90 to 99.9%), therebyproviding a copper foil.

It is important here to control the 60 degree gloss of the copper foilfor producing graphene to 500% or more. As one method to perform this,an oil film equivalent will be 18000 or less both at a final pass of thefinal cold rolling and a previous pass before the final pass of thefinal cold rolling.

A rolled copper foil is generally processed at high speed with oillubrication. When a lubricated oil film becomes thinner, shear banddeformation is prone to be dominant. This is a common phenomenon whichapplies to typical metals. The shear band is not necessarily preferableto the growth of the crystal grains when annealed. High and low orshallow and deep of the shear band can be presented by the gloss on thesurface of the copper foil. Specifically, as the phenomenon uponrolling, an oil pit (irregularity) is generated on a rolling processedsurface when the oil film that is introduced between the roll and thematerial is thick. When the oil film is thin, an area that is contactedwith the rolling roll on the surface of the material is increased. As aresult, free deformation is limited, the oil pit is not grown, a smoothsurface profile of the rolling roll is transferred and a smooth surfaceis formed. Because of this, as an indicator of the thin oil film, theoil film equivalent is limited to 18000 or less. If the oil filmequivalent exceeds 18000, the 60 degree gloss on the surface of thecopper foil is less than 500%.

The oil film equivalent is represented by the following equation:(Oil film equivalent amount)={(rolling oil viscosity, kinetic viscosityat 40° C., cSt)×(rolling speed; m/min)}/{(yield stress of material;kg/mm²)×(roll angle of bite; rad)}

In order to limit the oil film equivalent to 18000 or less, it ispreferable that the rolling oil viscosity (kinetic viscosity at 40° C.)is low, the rolling speed is low, and the roll angle of bite(corresponding to a rolling reduction) is high. For example, by arolling roll adjusted to have a roll diameter of 250 mm or less andsurface roughness Ra_(roll) of 0.1 μm or less (preferably 0.01 to 0.04μm, more preferably 0.01 to 0.02 μm), rolling oil having a viscosity of3 to 8 cSt (preferably 3 to 5 cSt, more preferably 3 to 4 cSt) is used.A rolling speed may be 100 to 500 m/min (preferably 200 to 450 m/min,more preferably 250 to 400 m/min), and the rolling reduction per passmay be 10 to 60%. The roll angle of bite is, for example, 0.001 to 0.04rad, preferably 0.002 to 0.03 rad, more preferably 0.003 to 0.03 rad.

If the surface roughness Ra_(roll) of the rolling roll exceeds 0.1 μm,the irregularity of the roll surface is transferred and smoothness ofthe material surface is impaired. By rolling under the above-describedconditions, a surface flatness having no oil pit can have a wide area.If the viscosity of the rolling oil exceeds 8 cSt, the oil filmequivalent is increased, thereby providing no surface gloss. On theother hand, if the oil film equivalent is less than 3 cSt, rollingresistance is too increased to increase the rolling reduction. If therolling speed exceeds 500 m/min, the oil amount introduced is increased,thereby decreasing the gloss. On the other hand, if the rolling speed isless than 100 m/min, the rolling reduction is not sufficiently providedand it is inconvenience from the standpoint of the productivity.

If the rolling reduction exceeds 99.9%, work hardening is accelerated tolose deformation capability, and the rolling reduction in the last passis not ensured. On the other hand, if the rolling reduction is less than80%, a rolling texture is not grown, thereby providing no surfaceflatness. If the roll angle of bite exceeds 0.04 rad, a differencebetween a roll peripheral speed and a material speed becomes great tolose the smoothness of the material surface. On the other hand, the rollangle of bite is less than 0.002 rad, the oil enters between the rollingroll and the material to be rolled and the amount of the oil is toogreat to lubricate, thereby decreasing the gloss.

The rolling reduction per pass is, for example, 20 to 40%, preferably 20to 35%, more preferably 25 to 35%. If the rolling reduction exceeds 35%,the shear band is grown to produce the oil pit, thereby decreasing thegloss. On the other hand, if the rolling reduction is less than 20%, thenumber of passes increases to degrade the productivity.

Furthermore, as another method to control the 60 degree gloss of thecopper foil for producing graphene to 500% or more, a materialtemperature is increased during the final cold rolling. When thematerial temperature is increased, dislocation recovery is induced toresist the shear band deformation. The material temperature has no sensewhen oil lubricity is lost or the copper foil is re-crystallized, andmay be 120° C. or less, preferably 100° C. or less. If the materialtemperature is 50° C. or less, there is almost no effect to prevent theshear band deformation.

By the above-described methods, it is possible to control the 60 degreegloss of the copper foil for producing graphene to 500% or more. Whenthe 60 degree gloss of the copper foil is 500% or more, it is found thatthe crystal grain size after annealing is 200 μm or more. This may bebecause the crystal growth after annealing is promoted by controllingthe oil film equivalent or the material temperature during the finalcold rolling to resist the shear band deformation as described above.

Controlling the 60 degree gloss of the copper foil for producinggraphene to 500% or more is not limited to the above-described methods.

Method of Producing Graphene

Next, referring to FIG. 1, a method of producing graphene according tothe embodiment of the present invention will be described.

First, the above-described copper foil 10 for producing graphene of thepresent invention is placed in a chamber (such as a vacuum chamber) 100and is heated by a heater 104. At the same time, the pressure in thechamber 100 is reduced or the chamber 100 is vacuum-evacuated. Then, acarbon-containing gas G is fed to the chamber 100 through a gas supplyinlet 102 (FIG. 2(a)). As the carbon-containing gas G, carbon dioxide,carbon monoxide, methane, ethane, propane, ethylene, acetylene, alcoholor the like is cited, but is not limited thereto. One or more of thesegases may be mixed. The copper foil 10 for producing graphene may beheated at a decomposition temperature of the carbon-containing gas G ormore. For example, the temperature can be 1000° C. or more.Alternatively, the carbon-containing gas G may be heated at thedecomposition temperature or more within the chamber 100, and thedecomposed gas may bring into contact with the copper foil 10 forproducing graphene.

Thus, the decomposition gas (carbon gas) forms graphene 20 on thesurface of the copper foil 10 for producing graphene (FIG. 2(b)).

Then, the copper foil 10 for producing graphene is cooled to normaltemperature, a transfer sheet 30 is laminated on the surface of thegraphene 20, and the graphene 20 is transferred to the transfer sheet30. Next, the laminate is continuously immersed into an etching tank 110via a sink roll 120, and the copper foil 10 for producing graphene isremoved by etching (FIG. 2 (c)). In this way, the graphene 20 laminatedon the predetermined transfer sheet 30 can be produced.

In addition, the laminate from which the copper foil 10 for producinggraphene is removed is pulled up, and a substrate 40 is laminated on thegraphene 20. While the graphene 20 is transferred to the substrate 40,the transfer sheet 30 is removed, whereby the graphene 20 laminated onthe substrate 40 can be produced.

As the transfer sheet 30, a variety of resin sheets (a polymer sheetsuch as polyethylene, polyurethane etc.) can be used. As an etchingliquid for etching and removing the copper foil 10 for producinggraphene, a sulfuric acid solution, a sodium persulfate solution, ahydrogen peroxide and sodium persulfate solution, or a solution wheresulfuric acid is added to hydrogen peroxide can be, for example, used.As the substrate 40, an Si, SiC, Ni or Ni alloy can be, for example,used.

EXAMPLE Preparation of Sample

A cooper ingot having a composition shown in Table 1 was prepared, washot rolled at 800 to 900° C., and was annealed in a continuous annealingline at 300 to 700° C. and cold rolled, which was repeated one time, toprovide a rolled sheet having a thickness of 1 to 2 mm. The rolled sheetwas annealed and re-crystallized in the continuous annealing line at 600to 800° C., and was finally cold rolled to a thickness of 7 to 50 μm ofa rolling reduction of 95 to 99.7% to provide each copper foil inExamples 1 to 15 and Comparative Examples 1 to 9.

Here, the oil film equivalents were adjusted to the values shown inTable 1 both at a final pass of the final cold rolling and a previouspass before the final pass of the final cold rolling.

The oil film equivalent is represented by the following equation:(Oil film equivalent amount)={(rolling oil viscosity, kinetic viscosityat 40° C., cSt)×(rolling speed; m/min)}/{(yield stress of material;kg/mm²)×(roll angle of bite; rad)}

Measurement of 60 Degree Gross

The copper foils in Examples 1 to 15 and Comparative Examples 1 to 9were final cold rolled and were heated at 1000° C. for 1 hour in anatmosphere containing 20% by volume or more of hydrogen and balanceargon. Thereafter, the 60 degree gross on each surface was measured.

The 60 degree gross was measured using a gloss meter in accordance withJIS-Z8741-1997 (trade name “PG-1M” manufactured by Nippon DenshokuIndustries Co., Ltd.)

Measurement of Surface Roughness (Ra, Rz, Sm)

The copper foils in Examples 1 to 15 and Comparative Examples 1 to 9were final cold rolled and were heated at 1000° C. for 1 hour in anatmosphere containing 20% by volume or more of hydrogen and balanceargon. Thereafter, the surface roughness of each was measured.

A contact roughness meter (trade name “SE-3400” manufactured by KosakaLaboratory Ltd.) was used to measure an arithmetic mean roughness (Ra;μm) in accordance with JIS-B0601-1994 was measured. As to an oil pitdepth Rz, a ten point height of roughness profile was measured inaccordance with JIS B0601-1994. Under the conditions of a measurementsampling length of 0.8 mm, an evaluation length of 4 mm, a cut off valueof 0.8 mm and a feed rate of 0.1 mm/sec, ten measurements were done inparallel with a rolling direction at different measurement positions,and values for ten measurements were determined in each direction. As toa mean distance of the irregularities (Sm; mm), under the conditions ofa measurement sampling length of 0.8 mm, an evaluation length of 4 mm, acut off value of 0.8 mm and a feed rate of 0.1 mm/sec, ten measurementswere done in parallel with a rolling direction at different measurementpositions, and values for ten measurements were determined in eachdirection. The Sm is defined as “Mean width of the profile elements” byJIS B0601-2001 (in accordance with ISO4287-1997) that represents asurface texture by a profile curve method, and refers to an average ofprofile lengths of respective irregularities in a sampling length.

Measurement of Average Crystal Grain Size

For each copper foil in Examples 1 to 15 and Comparative Examples 1 to9, the average crystal grain size was measured with a cutting method byJIS H0501-1986.

Production of Graphene

The copper foil (horizontal and vertical 100×100 mm) in each Example wasplaced in a vacuum chamber, and heated at 1000° C. Under vacuum(pressure: 0.2 Torr), methane gas was fed into the vacuum chamber (fedgas flow rate: 10 to 100 cc/min), the copper foil was heated to 1000° C.for 30 minutes and held for 1 hour to grow graphene on the surface ofthe copper foil.

In each Example, graphene was tried to be produced ten times under theabove-described conditions, and the surface of the copper foil wasobserved by the atomic force microscope (AFM) for graphene. Whenscale-like irregularities were observed on the whole surface by the AFM,graphene might be produced. Based on the number of times of the grapheneproduction when graphene was tried to be produced ten times, a yield wasevaluated by the following rating: The rating “Excellent”, “Good”, or“Not bad” may not have practical problems.

Excellent: Graphene was produced five times or more, when graphene wastried to be produced ten times

Good: Graphene was produced four times, when graphene was tried to beproduced ten times

Not bad: Graphene was produced three times, when graphene was tried tobe produced ten times

Bad: Graphene was produced two times or less, when graphene was tried tobe produced ten times

Table 1 shows the obtained result. In Table 1, G60_(RD) and G60_(TD)represent 60 degree gloss in a rolling direction and a directiontransverse to rolling direction, respectively. GS shows the averagecrystal grain size.

Also in Table 1, “TPC” in Examples 1 to 7, 14 and 15 and ComparativeExamples 1 to 3, 7 and 9 represents tough pitch copper in accordancewith JIS-H3100-2000. “OFC” in Examples 9 to 12 and Comparative Examples4 to 6 and 8 represents oxygen free copper in accordance withJIS-H3100-2000. TPC in Example 13 represents tough pitch copper inaccordance with JIS-H3250-2000. OFC in Example 8 represents oxygen freecopper in accordance with JIS-H3510-1992.

In view of this, “OFC+Sn 1200 ppm” in Comparative Example 8 representsthat 1200 wt ppm of Sn was added to oxygen free copper in accordancewith JIS-H3100-2000.

TABLE 1 Oil film Properties after final rolling equivaltent Surfaceamount Sheet roughness at final thickness 60 degree gloss (μm)Composition (wtppm) cold rolling (μm) G60_(RD) G60_(TD) Ra Rz RsmExample 1 TPC + Ag190 ppm 15,000 7 567 557 0.04 0.25 10.182 Example 2TPC + Ag190 ppm 15,000 12 565 555 0.04 0.25 10.171 Example 3 TPC + Ag190ppm 15,000 35 569 559 0.03 0.25 10.202 Example 4 TPC + Ag190 ppm 15,00050 567 556 0.04 0.25 10.172 Example 5 TPC + Ag100 ppm 15,000 12 542 5300.03 0.27 10.385 Example 6 TPC + Ag300 ppm 15,000 15 581 569 0.03 0.239.857 Example 7 TPC-Ag430 ppm 15,000 10 560 543 0.04 0.24 10.118 Example8 OFC + Sn50 ppm 12,000 18 593 578 0.03 0.21 10.001 Example 9 OFC +Sn300 ppm 12,000 30 577 571 0.030 0.26 11.003 Example 10 OFC-Sn470 ppm12,000 18 567 552 0.034 0.28 9.987 Example 12 OFC-Sn80 ppm—Ag70 ppm12,000 40 585 592 0.027 0.22 10.087 Example 12 OFC 12,000 50 560 5550.03 0.24 10.887 Example 13 TPC 15,000 35 531 520 0.04 0.29 11.254Example 14 TPC 17,000 18 505 502 0.04 0.29 11.301 Example 15 TPC + Ag190ppm 10,000 12 630 625 0.010 0.105 12.421 Comparative TPC + Ag190 ppm25,000 12 135 127 0.15 0.83 10.461 Example 1 Comparative TPC + Ag100 ppm25,000 18 107 158 0.19 0.98 9.888 Example 2 Comparative TPC + Ag300 ppm28,000 35 95 142 0.21 0.79 9.521 Example 3 Comparative OFC + Sn50 ppm25,000 10 145 145 0.17 0.75 9.447 Example 4 Comparative OFC + Sn300 ppm23,000 12 202 190 0.12 0.69 9.883 Example 5 Comparative OFC 25,000 35131 137 0.18 0.78 10.122 Example 6 Comparative TPC 30,000 18 94 108 0.230.81 9.556 Example 7 Comparative OFC + Sn1200 ppm 23,000 50 225 230 0.110.66 10.226 Example 8 Comparative TPC 21,000 12 280 272 0.09 0.54 9.722Example 9 Properties after heating at 1000° C. Surface roughness 60degree gloss (μm) GS Yield of G60_(RD) G60_(TD) Ra Rz Rsm (μm) grapheneExample 1 588 581 0.032 0.206 18.98 950 Excellent Example 2 586 5790.033 0.209 18.96 950 Excellent Example 3 590 583 0.031 0.204 19 950Excellent Example 4 588 580 0.032 0.208 18.97 950 Excellent Example 5555 542 0.028 0.244 18.23 935 Excellent Example 6 591 580 0.030 0.21516.88 910 Excellent Example 7 587 578 0.033 0.234 16 700 Good Example 8601 590 0.022 0.201 17.21 1120 Excellent Example 9 580 577 0.027 0.25319.2 1030 Excellent Example 10 576 569 0.029 0.255 18.55 405 GoodExample 12 595 603 0.022 0.208 18.12 980 Excellent Example 12 569 5610.024 0.219 19.02 1000 Excellent Example 13 547 528 0.034 0.270 19.55900 Excellent Example 14 511 507 0.036 0.281 19.02 250 Not bad Example15 645 641 0.009 0.095 22.326 1350 Excellent Comparative 152 135 0,0910.419 20.5 110 Bad Example 1 Comparative 120 168 0.104 0.574 20.02 130Bad Example 2 Comparative 108 152 0.152 0.472 19.54 120 Bad Example 3Comparative 155 154 0.110 0.471 18.47 130 Bad Example 4 Comparative 220196 0.085 0.398 19.02 150 Bad Example 5 Comparative 138 147 0.109 0.51120.01 190 Bad Example 6 Comparative 99 117 0.154 0.597 19.52 110 BadExample 7 Comparative 230 239 0.077 0.416 20.95 100 Bad Example 8Comparative 285 279 0.069 0.401 18.88 175 Bad Example 9

As apparent from Table 1, in each of Examples 1 to 15 where 60 degreegloss on the surface of the copper foil was 500% or more, and theaverage crystal grain size after heating at 1000° C. for 1 hour in anatmosphere containing 20% by volume or more of hydrogen and balanceargon, the production yield of graphene was excellent.

In particular, in each of Examples 1 to 6, 8, 9, 11 to 13 and 15 wherethe average crystal grain size after heating at 1000° C. for 1 hour inan atmosphere containing 20% by volume or more of hydrogen and balanceargon was 900 μm or more, the production yield of graphene was mostexcellent. Also, in each of Examples 7 and 10 where the average crystalgrain size after heating at 1000° C. for 1 hour in an atmospherecontaining 20% by volume or more of hydrogen and balance argon was 400to 900 μm, the production yield of graphene was better as compared withthat in Example 14 where the average crystal grain size was less than400 μm.

On the other hand, in each of Comparative Examples 1 to 9 where the oilfilm equivalent exceeded 18000 both at a final pass of the final coldrolling and a previous pass before the final pass of the final coldrolling, and 60 degree gloss on the surface of the copper foil was lessthan 500%, the production yield of graphene was poor. Also, in each ofComparative Examples 1 to 9, the average crystal grain size afterheating at 1000° C. for 1 hour in an atmosphere containing 20% by volumeor more of hydrogen and balance argon was less than 200 μm. It isconsidered that the oil film equivalent at final cold rolling was toohigh to cause the shear band, thereby suppressing the grow of thecrystal grains.

EXPLANATION OF REFERENCE NUMERALS

-   10 copper foil for producing graphene-   20 graphene-   30 transfer sheet

What is claimed is:
 1. A rolled copper foil for producing graphene,having 60 degree gloss of 500% or more in a rolling direction and adirection transverse to the rolling direction, and an average crystalgrain size of 200 μm or more after heating at 1000° C. for 1 hour in anatmosphere containing 20% by volume or more of hydrogen and balanceargon.
 2. The rolled copper foil for producing graphene according toclaim 1, wherein the average crystal grain size is 400 μm or more. 3.The rolled copper foil for producing graphene according to claim 1,wherein the average crystal grain size is 900 μm or more.
 4. The rolledcopper foil for producing graphene according to claim 1, wherein asuperficial arithmetic mean roughness Ra is 0.05 μm or less.
 5. A rolledcopper foil for producing graphene, having an average crystal grain sizeof 200 μm or more after heating at 1000° C. for 1 hour in an atmospherecontaining 20% by volume or more of hydrogen and balance argon, andwherein a superficial arithmetic mean roughness Ra is 0.05 μm or less.6. The rolled copper foil for producing graphene according to claim 5,wherein the superficial arithmetic mean roughness Ra is 0.03 μm or less.7. The rolled copper foil for producing graphene according to claim 1,prepared from a copper composition consisting of tough pitch copper inaccordance with JIS-H3100-2000 or JIS-H3250-2000; consisting of oxygenfree copper in accordance with JIS-H3100-2000 or JIS-H3510-1992; orconsisting of a composition wherein 0.050% by mass or less of one ormore elements selected from the group consisting of Sn and Ag is addedto the tough pitch copper or the oxygen free copper.
 8. A method ofproducing graphene using the rolled copper foil for producing grapheneaccording to claim 1, comprising the steps of: heating the rolled copperfoil for producing graphene while providing a carbon-containing gas toform graphene on a surface of the heated rolled copper foil; andlaminating a transfer sheet on the surface of the graphene, and etchingand removing the rolled copper foil for producing graphene whiletransferring the graphene to the transfer sheet.
 9. The rolled copperfoil of according to claim 1, having an oil film equivalent upon finalrolling of 18000 or less.